Article with buffer layer and method of making the same

ABSTRACT

A method of forming a coating layer on a glass substrate in a glass manufacturing process includes: providing a first coating precursor material for a selected coating layer composition to at least one multislot coater to form a first coating region of the selected coating layer; and providing a second coating precursor material for the selected coating layer composition to the multislot coater to form a second coating region of the selected coating layer over the first region. The first coating precursor material is different than the second precursor coating material.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to Provisional Application No.62/131,938, filed Mar. 12, 2015, which is herein incorporated byreference in its entirety.

NOTICE OF GOVERNMENT SUPPORT

This invention was made with Government support under Contract No.DE-EE0004736 awarded by the Department of Energy. The United Statesgovernment may have certain rights in this invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to electronic devices, for examplesolar cells, and to methods of making the same.

2. Technical Considerations

A solar cell or photovoltaic (PV) cell is an electronic device thatdirectly converts sunlight into electricity. Light shining on the solarcell produces both a current and a voltage to generate electric power.In a solar cell, photons from sunlight are adsorbed by a semiconductingmaterial. Electrons are knocked loose from their atoms, causing anelectric potential difference. Current flows through the semiconductormaterial to cancel the potential difference. Due to the specialcomposition of solar cells, the electrons are only allowed to move in asingle direction.

A typical solar cell includes a glass substrate (cover plate) over whichis provided a barrier layer, a transparent conductive oxide contactlayer, and a semiconductor layer. A rear metallic layer acts as areflector and back contact Light scattering or “haze” is used to traplight in the active region of the cell. The more light that is trappedin the cell, the higher the efficiency that can be obtained. However,the haze cannot be so great as to adversely impact upon thetransmittance of light through the conductive oxide layer.

It is also desirable that the conductive oxide layer is highlytransparent to permit the maximum amount of solar radiation to pass tothe semiconductor layer. As a general rule, the more photons that arriveat the semiconductor material, the higher the efficiency of the cell.Further, the conductive oxide layer should be highly conductive tofacilitate the transfer of electrons in the cell.

Articles such as Organic Light Emitting Diodes (OLED) and Light EmittingDiodes (LED) also utilize conductive oxide layers and would benefit fromenhanced haze and/or high transparency.

It would be desirable to provide a conductive oxide layer havingenhanced conductivity and/or light transmission and/or light scattering.It would be desirable to provide a method of modifying a conductiveoxide layer to affect (e.g., increase or decrease) one or more of thesefactors. It would be desirable to provide a conductive oxide layeruseful in solar cells, OLEDs, LEDs, as well as other electronic devices.It would be desirable to provide a coater useful for manufacturing solarcells, OLEDs, LEDs, as well as other electronic devices. It would bedesirable to provide a method of coating a glass substrate on one orboth major surfaces to provide a coated substrate useful in solar cells,OLEDs, LEDs, as well as other electronic devices. It would be desirableto provide an article and/or method to accomplish one or more of theabove results.

SUMMARY OF THE INVENTION

A solar cell comprises a first substrate having a first surface and asecond surface. An underlayer is located over the second surface. Afirst conductive layer is located over the underlayer. An overlayer islocated over the first conductive layer. A semiconductor layer islocated over the conductive oxide layer. A second conductive layer islocated over the semiconductor layer. The first conductive layercomprises a conductive oxide and at least one dopant selected from thegroup consisting of tungsten, molybdenum, niobium, and/or fluorine. Forexample, the first conductive layer can comprise tin oxide doped withtungsten.

A transparent conductive oxide layer for a solar cell comprises a metaloxide doped with tungsten. For example, tin oxide doped with tungsten.

A vapor deposition coater comprises a plenum assembly comprising aninlet plenum and an exhaust plenum; and a nozzle block comprising adischarge face. A discharge channel is in flow communication with theinlet plenum. An exhaust conduit is in flow communication with theexhaust plenum. The discharge channel is angled with respect to thedischarge face of the coating block.

A method of forming a coating on a glass substrate in a glassmanufacturing system comprises: providing a first coating precursormaterial to a first inlet plenum of a vapor deposition coater having adischarge face, wherein the first inlet plenum is in flow communicationwith a first discharge channel, and wherein the first discharge channeldefines a first discharge path; and providing a second coating precursormaterial to a second inlet plenum of the vapor deposition coaster,wherein the second inlet plenum is in flow communication with a seconddischarge channel, and wherein the second discharge channel defines asecond discharge path. The first discharge path intersects the seconddischarge path at a position selected from (a) above a surface of aglass ribbon or (b) at a surface of a glass ribbon or (c) below asurface of a glass ribbon.

A drawdown assembly comprises a receiver and a nanoparticle depositiondevice, such as a flame spray device, located adjacent a first sideand/or a second side of a glass ribbon path.

A method of forming a coated glass article in a drawdown processcomprises: locating at least one second coater adjacent a second side ofa glass ribbon path; optionally, locating at least one first coateradjacent a first side of the glass ribbon path; and using the secondcoater and optional first coater to apply a coating on a second side ofa glass ribbon and, optionally, on the first side of the glass ribbon.

A double sided coated article formed by a drawdown process comprises aglass substrate having a first surface and an opposed second surface. Afirst coating is formed over the first surface by a first chemical vapordeposition coater adjacent the first surface. A second coating is formedover the second surface by a second chemical vapor deposition coateradjacent the second surface. An internal light extraction region isformed on and/or in the second surface of the glass substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

A complete understanding of the invention will be obtained from thefollowing description when taken in connection with the accompanyingdrawing figures.

FIG. 1 is a side, sectional view of an article in the form of a solarcell incorporating features of the invention;

FIG. 2 is a side, sectional view of a chemical vapor deposition (CVD)coater incorporating features of the invention;

FIG. 3 is a side, sectional view of a nozzle block of a modified CVDcoater having a modified discharge channel arrangement; and

FIG. 4 is an end, sectional view of a glass drawdown processincorporating features of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Spatial or directional terms used herein, such as “left”, “right”,“inner”, “outer”, and the like, relate to the invention as it is shownin the drawing figures. It is to be understood that the invention canassume various alternative orientations and, accordingly, such terms arenot to be considered as limiting.

All numbers used in the specification and claims are to be understood asbeing modified in all instances by the term “about”. All rangesdisclosed herein are to be understood to encompass the beginning andending range values and any and all subranges subsumed therein. Theranges set forth herein represent the average values over the specifiedrange.

When referring to a layer of a coating, the term “over” means “fartherfrom the substrate”. For example, a second layer located “over” a firstlayer means that the second layer is located farther from the substratethan the first layer. The second layer can be in direct contact with thefirst layer or one or more other layers can be located between thesecond layer and the first layer.

The terms “polymer” or “polymeric” include oligomers, homopolymers,copolymers, and terpolymers.

All documents referred to herein are to be considered to be“incorporated by reference” in their entirety.

Any reference to amounts, unless otherwise specified, is “by weightpercent”.

The term “film” means a region having a desired or selected composition.A “layer” comprises one or more “films”. A “coating” is comprised of oneor more “layers”. The term “organic material” includes polymers as wellas small molecule organic materials that can be used to fabricateorganic opto-electronic devices.

The term “visible light” means electromagnetic radiation having awavelength in the range of 380 nm to 780 nm. The term “infraredradiation” means electromagnetic radiation having a wavelength in therange of greater than 780 nm to 100,000 nm. The term “ultravioletradiation” means electromagnetic energy having a wavelength in the rangeof 100 nm to less than 380 nm.

The terms “metal” and “metal oxide” include silicon and silica,respectively, as well as traditionally recognized metals and metaloxides, even though silicon may not be conventionally considered ametal. The term “curable” means a composition capable of polymerizing orcrosslinking. By “cured” is meant that the material is at least partlypolymerized or cross-linked, preferably fully polymerized orcross-linked. By “at least” is meant “greater than or equal to”. By “notmore than” is meant “less than or equal to”. The terms “upstream” and“downstream” refer to the direction of travel of the glass ribbon.

Haze and transmittance values herein are those determined using aHaze-Gard Plus hazemeter (commercially available from BYK-Gardner USA)or a Perkin Elmer Lamda 9 Spectrophotometer. Sheet resistance valueswere determined using a four-point probe (e.g., Nagy Instruments SD-600measurement device). Surface roughness values were determined using anInstrument Dimension 3100 Atomic Force Microscope.

The discussion of the invention may describe certain features as being“particularly” or “preferably” within certain limitations (e.g.,“preferably”, “more preferably”, or “even more preferably”, withincertain limitations). It is to be understood that the invention is notlimited to these particular or preferred limitations but encompasses theentire scope of the disclosure.

The invention comprises, consists of, or consists essentially of, thefollowing aspects of the invention, in any combination. Various aspectsof the invention are illustrated in separate drawing figures herein.However, it is to be understood that this is simply for ease ofillustration and discussion. In the practice of the invention, one ormore aspects of the invention shown in one drawing figure can becombined with one or more aspects of the Invention shown in one or moreof the other drawing figures.

The invention will be described with respect to a solar cell. However,it is to be understood that the invention could be practiced with otherdevices, for example, photovoltaic cells, organic light-emitting diodes,light emitting diodes, visual displays, and/or electronic switches.

An exemplary article, in the form of a solar cell 10, incorporatingfeatures of the invention is shown in FIG. 1. The solar cell 10 includesa first (outer) substrate 12 having a first (outer) major surface 14 anda second (Inner) major surface 16. By “outer” is meant the surfacefacing the incident radiation, e.g., sunlight. An underlayer 18 islocated over the second surface 16. A first conductive layer 20 islocated over the underlayer 18. An overlayer 22 is located over thefirst conductive layer 20. A semiconductor layer 24 is located over theoverlayer 22. A second conductive layer 26 is located over thesemiconductor layer 24. An optional second (inner) substrate 28 can belocated over the second conductive layer 26. For example, the secondsubstrate 28 can be connected to the second conductive layer 26 by apolymeric interlayer 30. An optional functional layer 32 can be locatedover the first surface 14 of the substrate 12. An optional internallight extraction region or layer 34 can be located in and/or on thesubstrate 12.

The first substrate 12 preferably has a high visible light transmission.By “high visible light transmission” is meant a visible lighttransmission at a reference wavelength of 550 nanometers (nm) and areference thickness of 2 mm of at least 85%, such as at least 87%. Forexample, such as at least 90%. For example, such as at least 91%. Forexample, such as at least 92%. For example, such as at least 93%.

The first substrate 12 can be a low iron glass. By “low iron” is meanthaving a total Iron content of less than 400 parts per million (ppm),such as less than 350 ppm. For example, the total iron content can beless than 300 ppm. For example, the total iron content can be less than200 ppm.

Examples of suitable materials for the first substrate 12 includesoda-lime silicate glass, for example, float glass.

Examples of glass that can be used for the invention include Starphire,Solarphire®, Solarphire® PV, and CLEAR™ glass, all commerciallyavailable from PPG Industries, Inc. of Pittsburgh, Pa.

The first substrate 12 can be of any desired thickness. For example, thefirst substrate 12 can have a thickness in the range of 0.5 mm to 10 mm,such as 1 mm to 10 mm, such as 1 mm to 4 mm. For example, the firstsubstrate 12 can have a thickness in the range of 2 mm to 3.2 mm.

The underlayer 18 can be a single layer, a homogeneous layer, a gradientlayer, or can include a plurality of layers. By “homogeneous layer” ismeant a layer in which the materials are randomly distributed throughoutthe coating. By “gradient layer” is meant a layer having two or morecomponents, with the concentration of the components varying (e.g.,continually changing or step change) as the distance from the substrate12 changes.

The underlayer 18 can be or can include an optional bottom optical layer36. The bottom optical layer 36 can include one or more metal oxidelayers. Examples of suitable oxide materials include oxides of silicon,titanium, aluminum, zirconium, phosphorus, hafnium, niobium, zinc,bismuth, lead, indium, tin, and/or alloys and/or mixtures thereof. Forexample, the bottom optical layer 38 can include an oxide of zinc,silicon, tin, aluminum, and/or titanium. For example, the bottom opticallayer 36 can include an oxide of zinc and/or tin.

A zinc target to sputter a zinc oxide film may include one or more othermaterials to improve the sputtering characteristics of the zinc target.For example, the zinc target can include up to 10 wt. %, such as up to 5wt %, of such a material. The resultant zinc oxide layer would include asmall percentage of an oxide of the added material, e.g., up to 10 wt. %of the material oxide, e.g., up to 5 wt. % of the material oxide. Alayer deposited from a zinc target having up to 10 wt. % of anadditional material to enhance the sputtering characteristics of thezinc target is referred to herein as “a zinc oxide layer” even though asmall amount of the added material (or an oxide of the added material)may be present. An example of such a material is tin.

The bottom optical layer 36 can include or can be a zinc stannate layer.By “zinc stannate” is meant a composition of the formula:Zn_(x)Sn_(1-x)O_(2-x) (Formula 1) where “x” varies in the range ofgreater than 0 to less than 1. For instance, “x” can be greater than 0and can be any fraction or decimal between greater than 0 to lessthan 1. A zinc stannate layer has one or more of the forms of Formula 1in a predominant amount. A zinc stannate layer in which x=⅔isconventionally referred to as “Zn₂SnO₄”.

The underlayer 18 can be or can include an optional sodium ion barrierlayer 38. Examples of suitable materials for the sodium ion barrierlayer 38 include metal oxide and metal alloy oxide materials. Forexample, oxides of silicon, titanium, aluminum, zirconium, phosphorus,hafnium, niobium, zinc, bismuth, lead, indium, tin, and alloys andmixtures thereof. For example, the sodium ion barrier layer 38 cancomprise silicon oxide. For example, the sodium ion barrier layer 38 cancomprise a mixture of at least silica and titania. For example, thesodium ion barrier layer 38 can comprise a mixture of silica, titania,and phosphorous oxide.

In FIG. 1, the sodium ion barrier layer 38 is illustrated over thebottom optical layer 36. However, alternatively, the sodium ion barrierlayer 38 could be positioned between the first substrate 12 and thebottom optical layer 36.

The underlayer 18 can comprise both the optional bottom optical layer 36and the optional sodium ion barrier layer 38. Alternatively, only one ofthe bottom optical layer 36 or the sodium ion barrier layer 38 may bepresent.

The underlayer 18 can have a thickness in the range of 10 nm to 500 nm,such as 20 nm to 400 nm. For example, such as 20 nm to 300 nm.

The first conductive layer 20 can be a single layer or can have multiplelayers or regions. The first conductive layer 20 comprises at least oneconductive oxide layer. For example, the first conductive layer 20 cancomprise a doped oxide layer. For example, the first conductive layer 20can include one or more metal oxide materials. For example, the firstconductive layer 20 can include one or more oxides of one or more of Zn,Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si, In, or analloy of two or more of these materials, such as zinc stannate. Forexample, the first conductive layer 20 can comprise tin oxide.

The first conductive layer 20 can include one or more dopant materials,such as but not limited to, F, In, Al, P, Cu, Mo, Ta, Ti, Ni, Nb, W, Ga,Mg, and/or Sb. For example, the dopant can be W, Mo, Nb, and/or F. Forexample, the dopant can be W or F. For example, the dopant can be W.

For example, the first conductive layer 20 can comprise W and an oxidematerial. For example, the first conductive layer can comprise tin oxidedoped with tungsten.

The dopant can be present in an amount less than 10 wt. %, such as lessthan 5 wt. %, such as less than 4 wt. %, such as less than 2 wt. %. Forexample, such as less than 1 wt. %. For example, less than 0.5 wt. %.For example, less than 0.1 wt. %.

The first conductive layer 20 can be a multilayer comprising a firstlayer or region and a second layer or region located over the firstlayer. For example, the first layer or region can be tungsten doped tinoxide. For example, the second layer or region can be fluorine doped tinoxide.

The first conductive layer 20 can have a thickness in the range of 150nm to 700 nm, such as 200 nm to 600 nm, such as 200 nm to 500 nm. Forexample, the first conductive layer 20 can have a thickness in the rangeof 200 nm to 450 nm.

The first conductive layer 20 can have a sheet resistance in the rangeof 8 ohms per square (Ω/□) to 25Ω/□, such 10Ω/□ to 20Ω/□. For example,such as 10Ω/□ to 17Ω/□.

The first conductive layer 20 can have a surface roughness (RMS) in therange of 5 nm to 60 nm, such as 5 nm to 40 nm, such as 5 nm to 30 nm,such as 10 nm to 30 nm, such as 10 nm to 20 nm. For example, such as 10nm to 15 nm. For example, such as 11 nm to 15 nm.

The overlayer 22 can be a homogeneous layer, a gradient layer, and/orcan include a plurality of layers or films.

The overlayer 22 can be or can include an optional buffer layer 42. Thebuffer layer 42 can improve the amount of electromagnetic energy to thesemiconductor layer 24.

The buffer layer 42 can include one or more oxide materials. Examples ofmaterials suitable for the buffer layer 42 include oxides of silicon,titanium, aluminum, zirconium, phosphorus, hafnium, magnesium, niobium,zinc, bismuth, gallium, lead, indium, and/or tin, and/or alloys and/ormixtures thereof. For example, the buffer layer 42 can comprise an oxideof zinc, indium, gallium, and/or tin. For example, the buffer layer 42can comprise tin oxide.

The buffer layer 42 can include one or more other materials doped withor alloyed with the oxide materials. Examples of the other materialsinclude zinc, magnesium, and/or tin.

For example, the buffer layer 42 can comprise zinc stannate. Forexample, the buffer layer 42 can comprise tin oxide doped with zincand/or magnesium. For example, the buffer layer 42 can comprise tinoxide doped with zinc.

The overlayer 22 can be or can include an optional insulating layer 44.Suitable materials for the insulating layer 44 include cadmium sulfideand/or a cadmium sulfate. An Insulating layer 44 is particularly usefulfor a cadmium telluride solar cell.

The overlayer 22 can comprise both the optional buffer layer 42 and theoptional Insulating layer 44. Alternatively, only one of the optionalbuffer layer 42 and the optional Insulating layer 44 may be present.

The overlayer 22 can have thickness in the range of 20 nm to 500 nm,such as 20 nm to 400 nm, such as 20 nm to 300 nm. For example, theoverlayer 22 can have thickness in the range of 20 nm to 200 nm.

The semiconductor layer 24 can comprise any conventional solar cellsemiconductor material. Examples of semiconductor material includemonocrystalline silicon, polycrystalline silicon, amorphous silicon,cadmium telluride, and/or copper indium celenide/sulfide.

The semiconductor layer 24 can have a thickness in the range of 200 nmto 1,000 nm, such as 200 nm to 800 nm, such as 300 nm to 500 nm. Forexample, such as 300 nm to 400 nm. For example, such as 350 nm.

The second conductive layer 26 is preferably a metal layer. Examples ofsuitable materials for the second conductive layer 26 include silver,barium, calcium, and magnesium. The second conductive layer 26 can be arelatively thick layer. For example, the second conductive layer 26 canbe opaque to light having a wavelength of 550 nm. By “opaque” is meanthaving a transmittance at a wavelength of 550 nm of less than 10%, suchas less than 5%, such as less than 3%. For example, such as less than1%. For example, 0%.

The optional second substrate 28 can be of any material described abovefor the first substrate 12. The first substrate 12 and second substrate28 can be of the same or different materials and can be of the same ordifferent thicknesses. For example, the second substrate 28 can comprisefloat glass.

The interlayer 30 can be an elastomeric polymer. Examples includeethylene vinyl acetate (EVA) and polyvinyl butyral (PVB).

The optional functional layer 32 can be a homogeneous layer, a gradientlayer, and/or can include a plurality of layers or films.

The optional functional layer 32 can be or can include an optionalantireflective layer 33. For example, the antireflective layer 33 can bea single layer or can comprise multiple films of antireflectivematerials and/or dielectric materials. Examples include metal oxides,oxides of metal alloys, nitrides, oxynitrides, or mixtures thereof.Examples of suitable metal oxides for the antireflective layer 33include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth,lead, indium, tin, and/or mixtures thereof. These metal oxides can havesmall amounts of other materials, such as manganese in bismuth oxide,tin in indium oxide, etc. Additionally, oxides of metal alloys or metalmixtures can be used, such as oxides containing zinc and tin (e.g., zincstannate), oxides of indium-tin alloys, silicon nitrides, siliconaluminum nitrides, or aluminum nitrides. Further, doped metal oxides,such as antimony or indium doped tin oxides or nickel or boron dopedsilicon oxides, can be used.

The antireflective layer 33 can have a thickness in the range of 5 nm to600 nm, such as 10 nm to 500 nm, such as 20 nm to 400 nm, such as 25 nmto 300 nm, such as 25 nm to 200 nm, such as 25 nm to 100 nm. Forexample, such as 25 nm to 50 nm. For example, such as 30 nm to 40 nm.

The optional functional layer 32 can be or can include an optionalexternal extraction layer 35. The external extraction layer 35 can beformed by a coating, such as a metal oxide coating, having a roughenedexterior surface. Examples of oxides useful for the external extractionlayer 35 include silica, alumina, zinc oxide, titania, zirconia, tinoxide, and/or mixtures thereof.

The external extraction layer 35 can have an average surface roughness(Ra) in the range of 5 nm to 500 nm, such as 5 nm to 500 nm, such as 50nm to 500 nm. For example, such as 50 nm to 200 nm. For example, such as100 nm to 200 nm.

The external extraction layer 35 can have a root mean square roughness(Rq) in the range of 100 nm to 250 nm. For example, such as 150 nm to200 nm.

The external extraction layer 35 can have a thickness in the range of 10nm to 500 nm, such as 50 nm to 500 nm. For example, such as 100 nm to500 nm. The external extraction layer 35 can be a single layer oroptionally a multilayer coating.

The optional functional layer 32 can comprise both the antireflectivelayer 33 and the external extraction layer 35. Alternatively, theoptional functional layer 32 can comprise only one of the antireflectivelayer 33 and the external extraction layer 35. Alternatively, thefunctional layer 32 may not be present.

One or more of the layers described above can be formed by anyconventional coating methods. Examples include spray pyrolysis; vapordeposition, such as chemical vapor deposition (CVD), packed-bedvaporization, flat-bed vaporization, and falling film vaporization;and/or magnetron sputtered vacuum deposition (MSVD). The layers can allbe formed by the same method or different layers can be formed bydifferent methods. For example, one or more of the layers can be formedby a CVD method while one or more other layers can be formed by MSVD orspray pyrolysis, for example.

For example, one or more of the layers or regions can be formed in afloat glass process. In another example, one or more of the layers orregions can be formed in a drawdown process.

In a float glass process, glass batch materials are melted in a furnaceand poured onto the top of a pool of molten metal in a float bath. Theglass melt spreads across the surface of the molten metal to form aglass ribbon. The glass ribbon exits the float bath and can be conveyedto a lehr for controlled cooling. One or more coaters, such as chemicalvapor deposition (CVD) coaters or flame spray devices, can be located inthe float bath.

A CVD coater 46 particularly well suited for applying volatileprecursors is shown in FIG. 2. The coater 46 includes a plenum assembly48 and a nozzle block 50. The nozzle block 50 has a discharge face 51directed toward the substrate to be coated, e.g., a glass ribbon 96. Theillustrated exemplary plenum assembly 48 has a first inlet plenum 52, asecond inlet plenum 54, and a third inlet plenum 56. The plenum assembly48 has a first exhaust plenum 58 and a second exhaust plenum 60. Theexemplary nozzle block 50 is connected to the plenum assembly 48, suchas by bolts.

The first inlet plenum 52 is in flow communication with a firstdischarge channel 62 having a first discharge outlet (slot) 64. Thesecond inlet plenum 54 is in flow communication with a second dischargechannel 66 having a second discharge outlet (slot) 68. The third inletplenum 56 is in flow communication with a third discharge channel 70having a third discharge outlet (slot) 72. Inlet mixing chambers 74 canbe located in the discharge channels.

A first exhaust conduit 76 extends from the discharge face 51 to thefirst exhaust plenum 58. A second exhaust conduit 78 extends from thedischarge face 51 to the second exhaust plenum 60. Exhaust chambers 80can be located in the exhaust conduits 76, 78.

In the illustrated example, the second discharge channel 66 isperpendicular to the discharge face 51 (i.e. a centerline axis of thesecond discharge channel 66 is perpendicular to the plane of thedischarge face 51). However, the first discharge channel 62 and thirddischarge channel 70 are angled with respect to the discharge face 51.The centerline axes of the first discharge channel 62 and the thirddischarge channel 70 intersect at a position below the discharge face51. Thus, the precursor vapors from the discharge outlets 64, 68, 72 arenot mixed until after discharge from the nozzle block 50. This isparticularly useful for volatile precursors where premixing of theprecursors would cause premature reaction.

The angle of one or more of the discharge channels 62, 66, 70 withrespect to the discharge face 51 can be changed so that the centerlineaxes of two or more of the discharge channels 62, 66, 70 intersect at adesired location (e.g., distance from the discharge face 51 and/orlocation with respect to an underlying substrate). For example,different nozzle blocks 50 having different discharge channel angles canbe provided. A nozzle block 50 having the desired discharge channelangles can be selected and bolted onto the plenum assembly 48.Alternatively, the nozzle block 50 can be formed by separate sections.The first exhaust conduit 76 can be in one section, the second exhaustconduit 78 can be in another section, and the discharge channels 62, 66,70 can be in a third section. The different sections can be individuallyconnectable with the plenum assembly 48. In this aspect, only thesection of the nozzle block 50 with the discharge channels 62, 66, 70would need to be replaced with a section having a desired dischargechannel angle. Alternatively, the first discharge channel 62, seconddischarge channel 66, and third discharge channel 70 can be located inseparate sections of the nozzle block 50 and movably connected, forexample slidably connected, to the plenum assembly 48. For example, withreference to FIG. 2, if the first discharge channel 62 is located in oneslidable section and the third discharge channel 70 is located in aseparate slidable section, sliding the slidable section containing thefirst discharge channel and/or the other slidable section containing thethird discharge channel 70 to the left or the right with reference toFIG. 2 would change the point of intersection of the centerlines of thedischarge channels. For example, sliding the section containing thefirst discharge channel 62 to the left and sliding the sectioncontaining the third discharge channel 70 to the right in FIG. 2 wouldincrease the distance of the point of intersection with respect to thedischarge face 51.

The angles of the discharge channels 62 and/or 70 can be varied suchthat the centerline axes intersect above the surface of the substrate,e.g., glass ribbon 96, or at the surface of the substrate, or below thesurface of the substrate. If the calculated intersection is below thesurface of the substrate, the vapors from the second discharge channel68 perpendicular to the discharge face 51 form a monolayer on the glassribbon and the material from the first discharge channel 62 and thirddischarge channel 70 react with it. In FIG. 2, the centerline axes ofthe discharge channels would intersect above the glass ribbon 96.

A central portion of a modified nozzle block 50 of a modified coater 47is shown in FIG. 3. In this modification, the first discharge outlet 64and third discharge outlet 72 are in flow communication with the seconddischarge channel 66 above the discharge face 51. Thus, the vapors fromthe three discharge channels mix before they are discharged from thesecond discharge outlet 68.

A coater 46, 47 having multiple discharge slots is particularly usefulfor applying one or more of the layers described above.

One or more of the above-described layers can be made by selectivedeposition of multiple precursor materials. For example, the firstconductive layer 20 can be formed using two or more different precursormaterials. Tin oxide coatings made with monobutyltin trichoride (MBTC)typically provide coatings with lower haze than other tin precursors,such as tin tetrachloride (TTC). However, the deposition efficiency forTTC is better than MBTC. Also, TTC tends to produce a coating with alower sheet resistance than a coating made from MBTC. Therefore, thefirst conductive layer 20 can initially be formed using MBTC (for haze)and then the precursor material switched to TTC to form the remainder ofthe first conductive layer 20. The overall efficiency is increased andthe resultant coating has the haze benefits of MBTC and the sheetresistance benefits of TTC.

For another example, the first conductive layer 20 can be formed usingMBTC and dibutyltin diacetate (DBTA). Tin coatings formed with MBTCtypically have a higher surface roughness than tin coatings formed withDBTA. However, DBTA has a slower deposition rate. If MBTC is mixed withDBTA, the resultant coating is smother than with MBTC alone and thedeposition rate is not as low as with DBTA alone.

The first conductive layer 20 can be formed having multiple layers andor regions. For example, a first region of the first conductive layer 20can be formed using a tin precursor and a tungsten precursor to providea tungsten doped tin oxide coating. For example, the tin precursor canbe MBTC or TTC. The tungsten precursor can be tungsten tetrachloride.For example, a second region of the first conductive layer 20 can thenbe deposited using a tin precursor and a fluorine precursor to provide afluorine doped tin oxide region.

The buffer layer 42 can be made using a tin precursor and a precursorfor zinc or magnesium. For example, the tin precursor can be MBTC orTTC. The zinc precursor can be diethylzinc (DEZ), dimethyl zinc (DMZ),zincacetyl acetate, or alkzinc alkoxide. The magnesium precursor can bebis(cyclopentadienyl)magnesium. For example, the buffer layer 42 can bemade using magnesium chloride mixed with MBTC.

The invention is not limited to the float glass process. One or more ofthe layers can be formed using a glass drawdown manufacturing process.In a drawdown process, molten glass is located in a receiver. The moltenglass flows out of the receiver and forms a glass ribbon, which movesdownwardly under the influence of gravity. Examples of drawdownprocesses include a slot drawdown process and a fusion drawdown process.In a slot drawdown process, the receiver is an elongated trough havingan open discharge slot in the bottom of the trough. Molten glass flowsthrough the discharge slot to form the glass ribbon. In a fusiondrawdown process, the receiver is a trough with an open top. Moltenglass flows out of the top of the trough, down the opposed outer sidesof the trough, and forms a glass ribbon under the trough. FIG. 4illustrates a drawdown assembly 81 configured as a fusion drawdownassembly. However, the drawdown assembly 81 could also be illustrated asa slot drawdown assembly.

In the exemplary fusion drawdown process illustrated in FIG. 4, moltenglass 82 is located in a receiver 83 in the form of a forming trough 86having a channel 84 and opposed sides 88, 90. The molten glass 82overflows the channel 84 and forms two glass films 92, 94 that flowdownwardly along the outer surfaces of the sides 88, 90, respectively,and join together under the trough 86 to form a glass ribbon 96. Theglass ribbon 96 moves downwardly under the force of gravity. Thevertical plane along which the glass ribbon 96 moves defines the glassribbon path 98 for the drawdown process. The glass ribbon path 98 has afirst side 106 and a second side 108, defining a first side 114 and asecond side 116 of the glass ribbon 96, respectively. As discussedabove, in a slot drawdown process, the receiver 83 would be in the formof an elongated trough having a slot in the bottom of the trough throughwhich the glass ribbon 96 emerges.

One or more coaters are located adjacent the glass ribbon 96 (i.e.adjacent the glass ribbon path 98). The coaters can be, for example, CVDcoaters and/or spray coaters and/or flame spray coaters and/or vaporcoaters. In the illustrated example, at least one coater 100 is locatedadjacent the second side 116 of the glass ribbon. Optionally, at leastone other coater 102 can be located adjacent the first side 114 of theglass ribbon 96. Thus, one or more of any of the above-described layerscan be formed on one or both surfaces of the glass ribbon 96. Forexample, the coaters 100, 102 can be conventional CVD coaters. Forexample, one or more of the coaters 100, 102 can be the coater 46 or thecoater 47 described above.

As shown in FIG. 1, the substrate 12 can include an optional internallight extraction region 34. The internal light extraction region 34 canbe formed by nanoparticles 40 incorporated on the second surface 16 ofthe substrate 12 and/or embedded in or incorporated into a region of theglass adjacent the second surface 16. Examples of suitable nanoparticles40 include, but are not limited to, oxide nanoparticles. For example butnot limited to alumina, titania, cerium oxide, zinc oxide, tin oxide,silica, and zirconia. Other examples include metallic nanoparticles. Forexample but not limited to iron, steel, copper, silver, gold, andtitanium. Further examples include alloy nanoparticles containing alloysof two or more materials. Additional examples include sulfide-containingnanoparticles and nitride-containing nanoparticles. These nanoparticlescan be incorporated into the substrate 12 (e.g., glass ribbon 96) at adepth in the range of 0 microns to 50 microns, such as 0 microns to 10microns, such as 0 micron to 5 microns. For example, such as 0 micronsto 3 microns.

The nanoparticles can be incorporated onto and/or into the substrate 12by propelling the nanoparticles from a coater toward the substrate 12.For example, in a float glass process, a flame spray device (orcombustion deposition device) can be mounted in the float chamberupstream of the CVD coater in the float process described above. Asuitable flame spray device is commercially available from Beneq-OyVantaa, Finland. Another suitable flame spray device is described in WO01/28941. In the flame spray device, coating materials are atomized,combusted, and then sprayed directly onto the hot glass ribbon. Theparticles are formed on and/or diffused into the surface of the ribbonor penetrate the surface and are incorporated into the upper portion ofthe glass ribbon. These particles, such as metal oxide nanoparticles,are present on the surface of the glass or are diffused into the glassand react with the glass matrix. This process can be practiced at anysuitable place in the float chamber but is believed to be more practicalat locations where the temperature of the glass ribbon is in the rangeof 400° C. to 1,000° C., such as 500° C. to 900° C., such as 500° C. to800° C., such as 600° C. to 800° C. For example, such as 700° C. to 800°C. After deposition of the nanoparticles on and/or in the surface, theglass ribbon can move under the CVD coater for the application of one ormore coating layers described above.

In the drawdown process illustrated in FIG. 4, one or more flame spraydevices 104 can be located adjacent the glass ribbon path 98. Forexample, the flame spray device(s) 104 can be located upstream of (i.e.,above) one or both of the coaters 100, 102. The nanoparticles 40 can bedeposited onto and/or into one or both sides 114, 1186 of the glassribbon 96. Subsequently, one or more of the coating layers describedabove can be applied over one or both sides 114, 116 of the glass ribbon96 by the coaters 100, 102. For example, the flame spray device 104 candeposit nanoparticles 40 onto and/or into the second side 116 of theglass ribbon 96 (e.g., corresponding to the second surface 16 of thesubstrate 12). Subsequently, one or more coaters 100 can apply one ormore of the underlayer 18, and/or first conductive layer 20, and/oroverlayer 22, and/or semiconductor layer 24, and/or second conductivelayer 26 over the second side 116 of the glass ribbon 96. One or moresecond coaters 102 can apply the optional functional layer 32 over thefirst side 114 of the glass ribbon 96.

The nanoparticles can be produced by any conventional method. In onespecific example, a liquid precursor can be heated in a vaporizer toform a vapor. The vapor can be directed to a reaction zone to form thedesired nanoparticles. Examples of liquid reactant vaporizers aredisclosed in U.S. Pat. Nos. 4,924,938, 5,356,451 and 7,730,747. Forexample, a metal chloride, such as titanium tetrachloride, can be heatedin a vaporizer to form a precursor vapor. The vapor can be directed toan applicator or a collector. For example, the vaporizer can beconnected to a flame spray device. The titanium tetrachloride vapor canbe hydrolyzed or oxidized to form titanium dioxide nanoparticles. Otherprecursors, such as organometallic compounds, can be used. Titaniumisopropoxide is an example of another material that can be vaporized toform titanium dioxide nanoparticles. The precursor stream may becomposed of one, two or more liquid reactant materials of differentcompositions so as to form nanoparticles having a pure composition, acomposition with mixed phases and/or compositions, or homogeneous alloysof a single or multiple phases. As will be appreciated by one skilled inthe art, the liquid reactant materials can be supplied in various ratiosto form nanoparticles of a desired composition. Further, one or moreprecursors may be supplied from a gaseous source to form nanoparticlesof a desired composition. Examples of this include supplying hydrogensulfide as a sulfur containing precursor to form a sulfide containingnanoparticle, or supplying ammonia (NH3) to form a nitride containingnanoparticle.

The invention can be described further in the following numberedclauses:

Clause 1: An article, for example a solar cell 10, comprising: a firstsubstrate 12 having a first surface 14 and a second surface 16; anunderlayer 18 located over the second surface 16; a first conductivelayer 20 over the underlayer 18; an overlayer 22 over the firstconductive layer 20; a semiconductor layer 24 over the first conductivelayer 20; and a second conductive layer 26 over the semiconductor layer24. The first conductive layer 20 comprises a conductive oxide and atleast one dopant selected from the group consisting of tungsten,molybdenum, niobium, and/or fluorine.

Clause 2: The article of clause 1, wherein the first substrate 12comprises low iron glass.

Clause 3: The article of clauses 1 or 2, wherein the underlayer 18comprises a sodium ion barrier layer 38 comprising silicon oxide.

Clause 4: The article of any of clauses 1 to 3, wherein the underlayer18 comprises a bottom optical layer 36 comprising an oxide of tin, zinc,silicon, aluminum, titanium, and/or mixtures thereof.

Clause 5: The article of any of clauses 1 to 4, wherein the underlayer18 comprises a sodium barrier layer 38 comprising silicon oxide and abottom optical layer 36 comprising oxides of tin and zinc.

Clause 6: The article of any of clauses 1 to 5, wherein the firstconductive layer 20 comprises tin oxide and tungsten.

Clause 7: The article of any of clauses 1 to 6, wherein the firstconductive layer 20 comprises a first layer comprising tin oxide andtungsten, and a second layer comprising tin oxide and fluorine.

Clause 8: The article of any of clauses 1 to 7, wherein the overlayer 22comprises a buffer layer 42 comprising tin oxide and at least one ofzinc, indium, gallium, magnesium, and nitrogen.

Clause 9: The article of any of clauses 1 to 8, wherein the overlayer 22comprises a buffer layer 42 comprising tin oxide and zinc.

Clause 10: The article of any of clauses 1 to 9, wherein the overlayer22 comprises an insulating layer 44 comprising cadmium sulfide and/orcadmium sulfate.

Clause 11: The article of any of clauses 1 to 10, wherein the overlayer22 comprises a buffer layer 42 comprising tin oxide and zinc and/ormagnesium, and an insulating layer 44 comprising cadmium sulfide and/orcadmium sulfate.

Clause 12: The article of any of clauses 1 to 11, wherein thesemiconductor layer 24 comprises cadmium telluride.

Clause 13: The article of any of clauses 1 to 12, wherein the secondconductive layer 26 comprises a metallic layer.

Clause 14: The article of any of clauses 1 to 13, wherein the secondconductive layer 26 comprises silver.

Clause 15: The article of any of clauses 1 to 14, including a secondsubstrate 28 over the second conductive layer 26, wherein the secondsubstrate 28 comprises glass.

Clause 16: The article of any of clauses 1 to 15, including an internallight extraction region 34 in and/or on the second surface 16 of thefirst substrate 12. The internal light extraction region 34 can comprisenanoparticles.

Clause 17: The article of any of clauses 1 to 16, including a functionallayer 32 over the first surface 14 of the first substrate 12, whereinthe functional layer 32 is selected from the group consisting of anantireflective layer 33 and an external light extraction layer 35.

Clause 18: The article of clause 17, wherein the antireflective layer 33comprises an oxide of a material selected from the group consisting oftitanium, zirconium, zinc, tin, and mixtures thereof.

Clause 19: The article of clauses 17 or 18, wherein the external lightextraction layer 35 is selected from the group consisting of silica,alumina, zinc oxide, titania, zirconia, tin oxide, and mixtures thereof.

Clause 20: The article of any of clauses 1 to 19, wherein the firstconductive layer 20 comprises a first region deposited from a firstprecursor material and a second region deposited from a second precursormaterial.

Clause 21: The article of clause 20, wherein the first precursormaterial comprises MBTC and the second precursor material is selectedfrom the group consisting of TTC and DBTA.

Clause 22: A transparent conductive oxide layer 20 for an article, forexample a solar cell 10, comprising a tin oxide and tungsten, preferablytungsten doped tin oxide.

Clause 23: A vapor deposition coater 46, 47 comprising: a plenumassembly 48 comprising at least one inlet plenum 52, 54, 56 and at leastone exhaust plenum 58, 60; and a nozzle block 50 comprising a dischargeface 51, at least one discharge channel 62, 66, 70 in flow communicationwith the at least one inlet plenum 52, 54, 56, and at least one exhaustconduit 76 in flow communication with the at least one exhaust plenum58, 60. The at least one discharge channel 62, 66, 70 is angled withrespect to the discharge face 51 of the nozzle block 50.

Clause 24: The vapor deposition coater 46, 47 of clause 23, wherein theat least one exhaust conduit 76 is angled with respect to the dischargeface 51.

Clause 25: The vapor deposition coater 48, 47 of clauses 23 or 24,including a first inlet plenum 52 in flow communication with a firstdischarge channel 62, a second inlet plenum 54 in flow communicationwith a second discharge channel 66, and a third inlet plenum 56 in flowcommunication with a third discharge channel 70, wherein at least one ofthe discharge channels 62, 66, 70 is angled with respect to thedischarge face 51 and at least one of the discharge channels 62, 66, 70is perpendicular to the discharge face 51.

Clause 26: The vapor deposition coater 46, 47 of any of clauses 23 to25, including a first exhaust plenum 58 in flow communication with afirst exhaust conduit 76 and a second exhaust plenum 60 in flowcommunication with a second exhaust conduit 78, wherein the firstexhaust conduit 76 and the second exhaust conduit 78 are angled withrespect to the discharge face 51.

Clause 27: The vapor deposition coater 46, 47 of any of clauses 23 to26, including at least one mixing chamber 74 located in the dischargechannels 62, 66 70 between the inlet plenums 52, 54, 56 and thedischarge face 51.

Clause 28: The vapor deposition coater 46, 47 of any of clauses 23 to27, including at least one exhaust chamber 80 located in the exhaustconduits 76, 78 between the exhaust plenum 58, 60 and the discharge face52.

Clause 29: The vapor deposition coater 46, 47 of clause 25, wherein thefirst discharge channel 62 has a first discharge outlet 64, the seconddischarge channel 66 has a second discharge outlet 68, and the thirddischarge channel 70 has a third discharge outlet 72, wherein the firstdischarge outlet 64, the second discharge outlet 68, and the thirddischarge outlet 72 are located on the discharge face 51.

Clause 30: The vapor deposition coater 46, 47 of clause 25, wherein thefirst discharge channel 62 has a first discharge outlet 64, the seconddischarge channel 66 has a second discharge outlet 68, and the thirddischarge channel 70 has a third discharge outlet 72, wherein the seconddischarge outlet 68 is located on the discharge face 51, and wherein thefirst discharge outlet 64 and the third discharge outlet 72 are in flowcommunication with the second discharge channel 66 at a distance fromthe discharge face 51, for example, above the discharge face 51.

Clause 31: The vapor deposition coater 46, 47 of any of clauses 23 to30, wherein the angle of at least one discharge channel 62, 66, 70 isadjustable with respect to the discharge face 51.

Clause 32: A method of forming a coating on a glass substrate, such as aglass ribbon 96, in a glass manufacturing process, comprising: providinga first coating precursor material to a first inlet plenum 52 of a vapordeposition coater 46, 47 having a discharge face 51, wherein the firstinlet plenum 52 is in flow communication with a first discharge channel62, and wherein the first discharge channel 62 defines a first dischargepath; and providing a second coating precursor material to a secondinlet plenum 54 of the vapor deposition coater 46, 47, wherein thesecond inlet plenum 54 is in flow communication with a second dischargechannel 70, and wherein the second discharge channel 70 defines a seconddischarge path; wherein the first discharge path intersects the seconddischarge path at a position selected from (a) above a surface of aglass ribbon 96 or (b) at a surface of a glass ribbon 96 or (c) below asurface of a glass ribbon 96.

Clause 33: A drawdown assembly 81, comprising: a receiver 83; and atleast one vapor coater 100, 102 located adjacent a first side 106 and/ora second side 108 of a glass ribbon path 98. For example, the receivercan comprise a forming trough 86 or an elongated trough having adischarge slot.

Clause 34: The drawdown assembly 81 of clause 33, including at least oneflame spray device 104 located adjacent the first side 106 and/or secondside 108 of the glass ribbon path 98.

Clause 35: The drawdown assembly 81 of clauses 33 or 34, including avapor coater 100 located on the second side 108, another vapor coater102 located on the first side 106, and a flame spray device 104 locatedupstream of the vapor coater 100 on the first side 106.

Clause 36: A method of forming a coated glass article in a drawdownprocess, comprising: locating at least one coater 100, 104 adjacent asecond side 108 of a glass ribbon path 98; locating at least one othercoater 102 adjacent a first side 106 of the glass ribbon path 98; andusing the coaters 100, 102, 104 to apply at least one coating on atleast one of the opposed sides of a glass ribbon 96.

Clause 37: The method of clause 36, wherein the at least one coater 100,104 comprises a chemical vapor deposition coater 100.

Clause 38: The method of clauses 36 or 37, wherein the at least oneother coater 102 comprises a chemical vapor deposition coater.

Clause 39: The method of any of clauses 36 to 38, further including atleast one flame spray coater 104 located on the second side 108, and,optionally, at least one flame spray coater 104 located on the firstside 106.

Clause 40: The method of any of clauses 36 to 39, wherein the at leastone coater 100, 102, 104 comprises a flame spray device 104 locatedupstream of a chemical vapor deposition coater 100.

Clause 41: A double sided coated article 110 formed by a drawdownprocess, comprising: a glass substrate 12 having a first surface 14 andan opposed second surface 16; a second coating 120 formed over thesecond surface 16 by a first chemical vapor deposition coater 100adjacent the first surface 114; and a first coating 118 formed over thefirst surface 114 by another chemical vapor deposition coater 102adjacent the first surface 114.

Clause 42: A buffer layer 42 for a solar cell 10, comprising: tin oxideand at least one of zinc, indium, gallium, and magnesium.

Clause 43: The buffer layer 42 of clause 42, wherein the buffer layer 42comprises tin oxide and zinc.

Clause 44: The buffer layer 42 of clause 42, wherein the buffer layer 42comprises tin oxide and magnesium.

Clause 45: An article, for example a solar cell 10, comprising: a firstsubstrate 12 having a first surface 14 and a second surface 16: anunderlayer 18 located over the second surface 16; a first conductivelayer 20 over the underlayer 18; an overlayer 22 over the firstconductive layer 20; a semiconductor layer 24 over the first conductivelayer 20; and a second conductive layer 26 over the semiconductor layer24. The overlayer 18 comprises a buffer layer 42 comprising tin oxideand at least one of zinc, indium, gallium, and magnesium.

Clause 46: The solar cell 10 of clause 45, wherein the buffer layercomprises tin oxide and zinc.

Clause 47: The article of clause 45, wherein the buffer layer 42comprises tin oxide and magnesium.

Clause 48: The article of any of clauses 45 to 47, including afunctional layer 32 over the first surface 14 of the substrate 12,wherein the functional layer 32 is selected from the group consisting ofan antireflective layer 33 and an external light extraction layer 35.

Clause 49: The article of any of clauses 45 to 48, wherein at least onelayer over the first surface 14 and at least one layer over the secondsurface 16 are formed in a glass drawdown process having at least onecoater 100, 102, 104 located on opposed sides of a glass ribbon path 98.

Clause 50: The article of any of clauses 45 to 49, wherein the firstconductive layer 20 comprises a conductive oxide and at least one dopantselected from the group consisting of tungsten, molybdenum, niobium,and/or fluorine.

Clause 51: The article of any of clauses 45 to 50, wherein the firstsubstrate 12 comprises low iron glass.

Clause 52: The article of any of clauses 45 to 51, wherein theunderlayer 18 comprises a sodium ion barrier layer 38 comprising siliconoxide.

Clause 53: The article of any of clauses 45 to 52, wherein theunderlayer 18 comprises a bottom optical layer 36 comprising an oxide oftin, zinc, silicon, aluminum, titanium, and/or mixtures thereof.

Clause 54: The article of any of clauses 45 to 53, wherein theunderlayer 18 comprises a sodium barrier layer 38 comprising siliconoxide and a bottom optical layer 36 comprising oxides of tin and zinc.

Clause 55: The article of any of clauses 45 to 54, wherein the firstconductive layer 20 comprises tin oxide and tungsten.

Clause 56: The article of any of clauses 45 to 55, wherein the firstconductive layer 20 comprises a first layer comprising tin oxide andtungsten, and a second layer comprising tin oxide and fluorine.

Clause 57: The article of any of clauses 45 to 56, wherein the overlayer22 comprises an insulating layer 44 comprising cadmium sulfide and/orcadmium sulfate.

Clause 58: The article of any of clauses 45 to 57, wherein the overlayer22 comprises a buffer layer 42 comprising tin oxide and zinc and/ormagnesium, and an insulating layer 44 comprising cadmium sulfide and/orcadmium sulfate.

Clause 59: The article of any of clauses 45 to 58, wherein thesemiconductor layer 24 comprises cadmium telluride.

Clause 60: The article of any of clauses 45 to 59, wherein the secondconductive layer 26 comprises a metallic layer.

Clause 61: The article of any of clauses 45 to 60, wherein the secondconductive layer 26 comprises silver.

Clause 62: The article of any of clauses 45 to 61, including a secondsubstrate 28 over the second conductive layer 26, wherein the secondsubstrate 28 comprises glass.

Clause 63: The article of any of clauses 45 to 62, including an internallight extraction region 34 in and/or on the second surface 16 of thesubstrate 12, wherein the internal light extraction region 34 comprisesnanoparticles 40.

Clause 64: The article of any of clauses 45 to 63, including afunctional layer 32 over the first surface 14 of the substrate 12,wherein the functional layer 32 is selected from the group consisting ofan antireflective layer 33 and an external light extraction layer 35.

Clause 65: The article of clause 64, wherein the antireflective layer 33comprises an oxide of a material selected from the group consisting oftitanium, zirconium, zinc, tin, and mixtures thereof.

Clause 66: The article of clauses 64 or 65, wherein the external lightextraction layer 35 is selected from the group consisting of silica,alumina, zinc oxide, titania, zirconia, tin oxide, and mixtures thereof.

Clause 67: The article of any of clauses 45 to 66, wherein the firstconductive layer 20 comprises a first region deposited from a firstprecursor material and a second region deposited from a second precursormaterial.

Clause 68: The article of clause 67, wherein the first precursormaterial comprises MBTC and the second precursor material is selectedfrom the group consisting of TTC and DBTA.

Clause 69: A transparent conductive oxide layer 20 for an electronicdevice, comprising: a tin oxide layer doped with a material selectedfrom the group consisting of tungsten, molybdenum, and niobium.

Clause 70: The transparent conductive oxide layer 20 of clause 69,wherein the transparent conductive oxide layer 20 comprises tin oxideand tungsten.

Clause 71: The transparent conductive oxide layer 20 of clauses 69 or70, wherein the electronic device is selected from the group consistingof a solar cell, a photovoltaic cell, an organic light emitting diode,and a light emitting diode.

Clause 72: A coated article 110, comprising: a first substrate 12 havinga first surface 14 and a second surface 16; a first coating 118 over thefirst surface 14; and a second coating 120 over the second surface 16.The second coating 120 comprises a first conductive layer 20 comprisingtin oxide doped with a material selected from the group consisting oftungsten, molybdenum, and niobium.

Clause 73: The coated article 110 of clause 72, wherein the firstconductive layer 20 comprises tin oxide doped with tungsten.

Clause 74: The coated article 110 of clauses 72 or 73, wherein at leastone layer over the first surface 14 and at least one layer over thesecond surface 16 are formed in a glass drawdown process having at leastone coater 100, 102, 104 on opposed sides of a glass ribbon path 98.

Clause 75: The coated article 110 of any of clauses 72 to 74, whereinthe coated article 110 is selected from the group consisting of a solarcell, a photovoltaic cell, an organic light emitting diode, and a lightemitting diode.

Clause 76: The coated article 110 of any of clauses 72 to 75, whereinthe second coating 120 comprises: an underlayer 18 located over thesecond surface 116; the first conductive layer 20 over the underlayer18; an overlayer 22 over the first conductive layer 20; a semiconductorlayer 24 over the first conductive layer 20; and a second conductivelayer 26 over the semiconductor layer 24.

Clause 77: The coated article 110 of clause 76, wherein the firstsubstrate 12 comprises low iron glass.

Clause 78: The coated article 110 of clauses 76 or 77, wherein theunderlayer 18 comprises a sodium ion barrier layer 38 comprising siliconoxide.

Clause 79: The coated article 110 of any of clauses 76 to 78, whereinthe underlayer 18 comprises a bottom optical layer 36 comprising anoxide of tin, zinc, silicon, aluminum, titanium, and/or mixturesthereof.

Clause 80: The coated article 110 of any of clauses 76 to 79, whereinthe underlayer 18 comprises a sodium barrier layer 38 comprising siliconoxide and a bottom optical layer 36 comprising oxides of tin and zinc.

Clause 81: The coated article 110 of any of clauses 76 to 80, whereinthe first conductive layer 20 comprises tin oxide and tungsten.

Clause 82: The coated article 110 of any of clauses 76 to 81, whereinthe first conductive layer 20 comprises a first layer comprising tinoxide and tungsten, and a second layer comprising tin oxide andfluorine.

Clause 83: The coated article 110 of any of clauses 76 to 82, whereinthe overlayer 22 comprises a buffer layer 42 comprising tin oxide and atleast one of zinc, indium, gallium, magnesium, and nitrogen.

Clause 84: The coated article 110 of any of clauses 76 to 83, whereinthe overlayer 22 comprises a buffer layer 42 comprising tin oxide andzinc.

Clause 85: The coated article 110 of any of clauses 76 to 84, whereinthe overlayer 22 comprises an insulating layer 44 comprising cadmiumsulfide and/or cadmium sulfate.

Clause 86: The coated article 110 of any of clauses 76 to 85, whereinthe overlayer 22 comprises a buffer layer 42 comprising tin oxide andzinc and/or magnesium, and an insulating layer 44 comprising cadmiumsulfide and/or cadmium sulfate.

Clause 87: The coated article 110 of any of clauses 76 to 86, whereinthe semiconductor layer 24 comprises cadmium telluride.

Clause 88: The coated article 110 of any of clauses 76 to 87, whereinthe second conductive layer 26 comprises a metallic layer.

Clause 89: The coated article 110 of any of clauses 76 to 88, whereinthe second conductive layer 26 comprises silver.

Clause 90: The coated article 110 of any of clauses 78 to 89, includinga second substrate 28 over the second conductive layer 26, wherein thesecond substrate 28 comprises glass.

Clause 91: The coated article 110 of any of clauses 76 to 90, includingan internal light extraction region 34 in and/or on the second surface16 of the substrate 12, wherein the internal light extraction region 34comprises nanoparticles 40.

Clause 92: The coated article 110 of any of clauses 76 to 91, includinga functional layer 32 over the first surface 14 of the substrate 12,wherein the functional layer 32 is selected from the group consisting ofan antireflective layer 33 and an external light extraction layer 35.

Clause 93: The coated article 110 of clause 92, wherein theantireflective layer 33 comprises an oxide of a material selected fromthe group consisting of titanium, zirconium, zinc, tin, and mixturesthereof.

Clause 94: The coated article 110 of clauses 92 or 93, wherein theexternal light extraction layer 35 is selected from the group consistingof silica, alumina, zinc oxide, titania, zirconia, tin oxide, andmixtures thereof.

Clause 95: The coated article 110 of any of clauses 76 to 94, whereinthe first conductive layer 20 comprises a first region deposited from afirst precursor material and a second region deposited from a secondprecursor material.

Clause 96: The coated article 110 of clause 95, wherein the firstprecursor material comprises MBTC and the second precursor material isselected from the group consisting of TTC and DBTA.

Clause 97: A method of making a making an article 110, such as a solarcell 10, in a glass drawdown process, comprising: locating at least onecoater 100, 104 adjacent a second side 108 of a glass ribbon path 98;optionally, locating at least one other coater 102, 104 adjacent a firstside 106 of the glass ribbon path 98; and applying a second coating overa second surface 116 of a glass ribbon 96, wherein the second coatingcomprises at least one of (i) a buffer layer 42 comprising tin oxide andat least one material selected from the group consisting of zinc,indium, gallium, and magnesium, and (ii) a transparent conductive oxidelayer 20 comprising tin oxide doped with a material selected from thegroup consisting of tungsten, molybdenum, and niobium.

Clause 98: The method of clause 97, wherein the buffer layer 42comprises tin oxide and zinc.

Clause 99: The method of clause 97, wherein the buffer layer 42comprises tin oxide and magnesium.

Clause 100: The method of any of clauses 97 to 99, wherein thetransparent conductive oxide layer 20 comprises tin oxide doped withtungsten.

Clause 101: A vapor deposition coater 46, 47, comprising: a nozzle block50 comprising a discharge face 51, at least one discharge channel 62,66, 70 in flow communication with at least one inlet plenum 52, 54, 56.An angle of the at least one discharge channel 62, 66, 70 is adjustablewith respect to the discharge face 51.

Clause 102: The vapor deposition coater 46, 47 of clause 101, includinga first discharge channel 62, a second discharge channel 66, and a thirddischarge channel 70, wherein at least one of the discharge channels 62,66, 70 is angled with respect to the discharge face 51 and at least oneof the discharge channels 62, 66, 70 is perpendicular to the dischargeface 51.

Clause 103: The vapor deposition coater 46, 47 of clauses 101 or 102,wherein the first discharge channel 62 has a first discharge outlet 64,the second discharge channel 66 has a second discharge outlet 68, andthe third discharge channel 70 has a third discharge outlet 72, whereinthe first discharge outlet 64, the second discharge outlet 66, and thethird discharge outlet 72 are located on the discharge face 51.

Clause 104: The vapor deposition coater 48, 47 of clauses 101 or 102,wherein the first discharge channel 62 has a first discharge outlet 64,the second discharge channel 66 has a second discharge outlet 68, andthe third discharge channel 70 has a third discharge outlet 72, whereinthe second discharge outlet 68 is located on the discharge face 51, andwherein the first discharge outlet 64 and the third discharge outlet 72are in flow communication with the second discharge channel 66 above thedischarge face 51.

Clause 105: A method of forming a coating layer on a glass substrate ina glass manufacturing process, comprising: providing a first coatingprecursor material for a selected coating layer composition to at leastone multislot coater 46, 47 to form a first coating region of theselected coating layer; and providing a second coating precursormaterial for the selected coating layer composition to at least onemultislot coater 46, 47 to form a second coating region of the selectedcoating layer over the first region. The first coating precursormaterial is different than the second precursor coating material.

Clause 106: The method of clause 105, wherein the glass manufacturingprocess is a float glass process and the at least one multislot coater46, 47 is located in a float bath.

Clause 107: The method of clause 105, wherein the glass manufacturingprocess is a glass drawdown process and the at least one multislotcoater 46, 47 is located adjacent a glass ribbon path 98.

Clause 108: The method of clause 107, wherein the glass manufacturingprocess is a glass drawdown process having a glass ribbon path 98comprising a first side 106 and a second side 108, wherein at least onemultislot coater 100 is located adjacent the first side 106 of the glassribbon path 98, and wherein at least one other multislot coater 102 islocated adjacent the second side 108 of the glass ribbon path 98.

Clause 109: The method of clause 107, wherein the glass manufacturingprocess is a glass drawdown process having a glass ribbon path 98comprising a first side 106 and a second side 108, wherein at least onemultislot coater 100 is located adjacent the second side 108 of theglass ribbon path 98, and wherein at least one other multislot coater102 is located adjacent the first side 106 of the glass ribbon path 98.

Clause 110: A method of forming a coating on a glass substrate in aglass manufacturing process, comprising: providing a first coatingprecursor material to a first discharge channel 62, 66, 70 having afirst discharge path; and providing a second coating precursor materialto a second discharge channel 62, 66, 70 having a second discharge path.The first discharge path intersects the second discharge path at aposition selected from (a) above a surface of a glass ribbon 96 or (b)at a surface of a glass ribbon 96 or (c) below a surface of a glassribbon 96.

It will be readily appreciated by those skilled in the art thatmodifications may be made to the invention without departing from theconcepts disclosed in the foregoing description. Accordingly, theparticular embodiments described in detail herein are illustrative onlyand are not limiting to the scope of the invention, which is to be giventhe full breadth of the appended claims and any and all equivalentsthereof.

What is claimed is:
 1. A method of forming a coating layer on a glasssubstrate in a glass manufacturing process, comprising: providing afirst coating precursor material to a first discharge channel having afirst discharge path, wherein the first coating precursor materialcomprises monobutyltin trichloride or tin tetrachloride; and providing asecond coating precursor material to a second discharge channel having asecond discharge path, wherein the first coating precursor material isdifferent than the second precursor coating material, and wherein thefirst discharge path intersects the second discharge path at a positionabove a surface of the glass substrate or at the surface of the glasssubstrate or below the surface of the glass substrate.
 2. The method ofclaim 1, wherein the glass manufacturing process is a float glassprocess and the first discharge channel is located in a float bath. 3.The method of claim 1, wherein the glass manufacturing process is aglass drawdown process.
 4. The method of claim 1, wherein the glassmanufacturing process is a glass drawdown process having a glass ribbonflow path comprising a first side and a second side, wherein at leastthe first coating precursor and the second precursor coating materialare provided on the second side of the glass ribbon flow path, andwherein the method further comprises providing a second coating to thefirst side of the glass ribbon flow path.
 5. The method of claim 1,wherein the coating layer is formed on the glass substrate by vapordeposition.
 6. The method of claim 1, wherein the second coatingprecursor material comprises tin tetrachloride or dibutyltin diacetateor tungsten tetrachloride.
 7. A method of making a coated glass articlein a glass drawdown process, comprising: positioning at least one firstcoater adjacent a first side of a glass ribbon flow path; positioning atleast one second coater adjacent a second side of the glass ribbon flowpath; depositing a first coating on a first side of a glass ribbon withthe at least one first coater; and depositing a second coating on asecond side of a glass ribbon with the second coater, wherein the atleast one first coating and the second coating are different, andwherein the at least one first coater comprises a chemical vapordeposition coater, wherein the at least one first coater comprises afirst discharge channel having a first discharge path and a seconddischarge channel having a second discharge path that intersects thefirst discharge path.
 8. The method of claim 7, wherein the at least onesecond coater comprises a chemical vapor deposition coater.
 9. Themethod of claim 7, wherein the at least one second coater comprises aflame spray coater.
 10. The method of claim 7, wherein the at least onesecond coater comprises a flame spray device located above a chemicalvapor deposition coater.
 11. The method of claim 7, wherein at least oneof the at least one first coater and the at least one second coatercomprises a multislot coater.
 12. The method of claim 7, wherein thesecond coating comprises at least one of (1) a buffer layer comprisingtin oxide and at least one material selected from the group consistingof zinc, indium, gallium, and magnesium, and (2) a transparentconductive oxide layer comprising tin oxide doped with a materialselected from the group consisting of tungsten, molybdenum, and niobium.13. The method of claim 12, wherein the buffer layer comprises tin oxideand zinc.
 14. The method of claim 12, wherein the buffer layer comprisestin oxide and magnesium.
 15. The method of claim 12, wherein thetransparent conductive oxide layer comprises tin oxide doped withtungsten.
 16. The method of claim 7 wherein the at least one secondcoater comprises a first discharge channel having a first discharge pathand a second discharge channel having a second discharge path thatintersects the first discharge path.
 17. The method of claim 16 whereinthe at least one second coater further comprises a third dischargechannel at an angle to a discharge face.
 18. The method of claim 7wherein the first coating or the second coating comprises tin oxidedoped with tungsten.